Understanding the hydroxyl adsorption behavior at Pt electrode surface in high-temperature alkaline solutions

Since the application in fuel cell,the electrochemical adsorption of hydroxyl has received considerable attention in recent years.While most research mainly focus on the room temperature,in this paper,the electrochemical adsorption of hydroxyl in alkaline solution at high temperature was investigated.An unusual oxidation peak was observed at-0.27 V,suggesting new behavior of hydroxyl adsorption occurred.As is known two kinds of cation hydrated clusters exist in alkaline solution,(H_(2)O)_(x-1)M^(+)-H_(2)O-O_(ad)H and(H_(2)O)_xM^(+)-O_(ad)H.For K^(+)and Cs^(+),the cluster shows unstable structure due to the weak interaction between hydrated cation and OH^(-)especially at high temperature.However,For Li^(+),Na^(+)the cluster structure would be stable,as the interaction force between the hydrated cation and OH^(-)is so strong.It was revealed that the unusual oxidation peak has some relationship with the(H_(2)O)_(x-1)M^(+)-H_(2)O-O_(ad)H cluster(K^(+)and Cs^(+))absorbed at Pt electrode surface.When the temperature was raised,(H_(2)O)_(x-1)M^(+)-H_(2)O-and-O_(ad)H was disconnected,then the O_(ad)H absorbed at Pt surface got oxidated.Based on the SEM observation,it was showed the unusual electrochemical oxidation reaction would generate platinum oxides,blocking the reactive sites at Pt electrode surface,thus reducing the electrochemical reactivity of Pt electrode.Accordingly,parameters of alkaline concentration and temperature were systematically studied,it was found that increase temperature or alkaline concentration was in favor of the unusual oxidation reaction.This study provides more understanding of hydroxyl adsorption behavior at Pt electrode surface for the high temperature water solution environment.

Polyaniline Formed in Alkaline Solution─A New Luminous Material

Electropolymerization of aniline in KOH solution and properties of the polymer are studied by using in situ reflex ellipsometry, cyclic voltammetry and fluorescence spectroscopic method. The change patterns of ellipsometric parameters and the thickness of film in the process of electropolymerization are investigated. The complex refractive indices and the fluorescence spectra of PAN indicate that the PAN is a new kind of luminous material.

Electrocatalytic Activity of Ni/C Electrodes Prepared by Metal Vapor Synthesis For Hydrogen Evolution in Alkaline Solution

The metal vapor synthesis (MVS) methed was used to prepare activatedcarbon supported nickel electrode. The electrocatalytic activity of the electrode forhydrogen evolution reaction(HGR) in alkaline solution was studied. Cathodicpolarization curves showed the electrocatalytic activity of Ni/C electrode prepared byMVS method was higher than that of the one prepared by conventional method.

Corrosion-wear behavior of nanocrystalline Fe88Si12 alloy in acid and alkaline solutions

The corrosion-wear behavior of a nanocrystalline Fe_（88）Si_（12） alloy disc coupled with a Si_3N_4 ball was investigated in acid（pH 3） and alkaline（pH 9） aqueous solutions. The dry wear was also measured for reference. The average friction coefficient of Fe_（88）Si_（12） alloy in the pH 9 solution was approximately 0.2, which was lower than those observed for Fe_（88）Si_（12） alloy in the pH 3 solution and in the case of dry wear. The fluctuation of the friction coefficient of samples subjected to the pH 9 solution also showed similar characteristics. The wear rate in the pH 9 solution slightly increased with increasing applied load. The wear rate was approximately one order of magnitude less than that in the pH 3 solution and was far lower than that in the case of dry wear, especially at high applied load. The wear traces of Fe_（88）Si_（12） alloy under different wear conditions were examined and analyzed by scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy. The results indicated that the tribo-chemical reactions that involve oxidation of the worn surface and hydrolysis of the Si_3N_4 ball in the acid solution were restricted in the pH 9 aqueous solution. Thus, water lubrication can effectively improve the wear resistance of nanocrystalline Fe_（88）Si_（12） alloy in the pH 9 aqueous solution.

Corrosion behavior of Cu/Al casting-rolled clad plates in different alkaline solution

The effect of pH value and different kinds of anions on the corrosion behavior of Cu/Al casting-rolled clad plates in the alkaline solution was evaluated by means of scanning electron microscopy(SEM),energy dispersive spectroscopy(EDS),X-ray diffraction(XRD),weight loss analysis,3D confocal laser scanning microscopy(CLSM)and electrochemical test.Results show the corrosion mainly occurs on the aluminum side.The corrosion resistance of the Cu/Al decreases as the pH value increases.When pH≥12,the dissolution of the film layer is faster than the passivation process.The addition of Cl^(-)ions reduces the corrosion resistance of the Cu/Al clad plates,which leads to pitting corrosion.The higher the concentration of Cl^(-)ions,the more prone the pitting to occur.The addition of SO_(4)^(2-)ions causes the denudation of the samples.The corrosion resistance of the Cu/Al is better in the alkaline solution containing NO_(3)^(-)ions than that in the solution containing Cl^(-)ions or SO_(4)^(2-)ions.When adding SO_(4)^(2-),NO^(3)^(-)and Cl^(-)to the pure alkaline solution,the corrosion resistance of the Cu/Al clad plates decreases.

Effects of applied potential on the stress corrosion cracking behavior of 7003 aluminum alloy in acid and alkaline chloride solutions

Potentiodynamic polarization tests and slow strain rate test（SSRT） in combination with fracture morphology observations were conducted to investigate the stress corrosion cracking（SCC） behavior of 7003 aluminum alloy（AA7003） in acid and alkaline chloride solutions under various applied potentials（Ea）. The results show that AA7003 is to a certain extent susceptible to SCC via anodic dissolution（AD） at open-circuit potential（OCP） and is highly susceptible to hydrogen embrittlement（HE） at high negative Ea in the solutions with p H levels of 4 and 11. The susceptibility increases with negative shift in the potential when Ea is less than-1000 m V vs. SCE. However, the susceptibility distinctly decreases because of the inhibition of AD when Ea is equal to-1000 m V vs. SCE. In addition, the SCC susceptibility of AA7003 in the acid chloride solution is higher than that in the alkaline solution at each potential. Moreover, the effect of hydrogen on SCC increases with increasing hydrogen ion concentration.

Investigation of aluminum gate CMP in a novel alkaline solution

Beyond 45 nm, due to the superior CMP performance requirements with the metal gate of aluminum in the advanced CMOS process, a novel alkaline slurry for an aluminum gate CMP with poly-amine alkali slurry is investigated. The aluminum gate CMP under alkaline conditions has two steps： stock polishing and fine polishing. A controllable removal rate, the uniformity of aluminum gate and low corrosion are the key challenges for the alkaline polishing slurry of the aluminum gate CMP. This work utilizes the complexation-soluble function of FA/O II and the preference adsorption mechanism of FA/O I nonionic surfactant to improve the uniformity of the surface chemistry function with the electrochemical corrosion research, such as OCP-TIME curves, Tafel curves and AC impedance. The result is that the stock polishing slurry （with SiO2 abrasive） contains 1 wt.% H2O2,0.5 wt.% FA/O II and 1.0 wt.% FA/O I nonionic surfactant. For a fine polishing process, 1.5 wt.% H2O2, 0.4 wt.% FA/O II and 2.0 wt.% FA/O I nonionic surfactant are added. The polishing experiments show that the removal rates are 3000 ±50 A/min and 1600 ± 60 A/dmin, respectively. The surface roughnesses are 2.05 ± 0.128 nm and 1.59 ± 0.081 nm, respectively. A combination of the functions of FA/O II and FA/O I nonionic surfactant obtains a controllable removal rate and a better surface roughness in alkaline solution.

Electrochemical quartz crystal microbalance study on Au-supported Pt adlayers for electrocatalytic oxidation of methanol in alkaline solution

Underpotential deposition(UPD) of Cu on an Au electrode followed by redox replacement reaction(RRR) of CuUPD with a Pt source(H2PtCl6 or K2PtCl4) yielded Au-supported Pt adlayers(for short,Pt(CuUPD-Pt4+)n/Au for H2PtCl6,or Pt(CuUPD-Pt2+)n/Au for K2PtCl4,where n denotes the number of UPD-redox replacement cycles).The electrochemical quartz crystal microbalance(EQCM) technique was used for the first time to quantitatively study the fabricated electrodes and estimate their mass-normalized specific electrocatalytic activity(SECA) for methanol oxidation in alkaline solution.In comparison with Pt(CuUPD-Pt2+)n/Au,Pt(CuUPD-Pt4+)n/Au exhibited a higher electrocatalytic activity,and the maximum SECA was obtained to be as high as 35.7 mA ?g?1 at Pt(CuUPD-Pt4+)3/Au.The layer-by-layer architecture of Pt atoms on Au is briefly discussed based on the EQCM-revealed redox replacement efficiency,and the calculated distribution percentages of bare Au sites agree with the experimental results deduced from the charge under the AuOx-reduction peaks.The EQCM is highly recommended as an efficient technique to quantitatively examine various electrode-supported catalyst adlayers,and the highly efficient catalyst adlayers of noble metals are promising in electrocatalysis relevant to biological,energy and environmental sciences and technologies.

POLAROGRAPHIC CHARACTERISTICS OF TELLURIUM(Ⅳ)IN ALKALINE DYE-ACID SOLUTION

Polarographic characteristics of Te(Ⅳ)-alkaline dye were investiga- ted at mercury electrode in acidic solution.It was found that the mechanism of the electrode process depended on the concentration of Te(Ⅳ).

Passivation kinetics of Mg-Nd-Gd-Zn-Zr(EV31A)and Mg-Y-Nd-Gd-Zr(WE43C)in NaOH solutions

Passivation kinetics of two Mg-RE alloys,such as Mg-Nd-Gd-Zn-Zr(EV31A),and Mg-Y-Nd-Gd-Zr(WE43C)were investigated in two different heat treated conditions(solution treated and overaged)in 0.01-1.0 M NaOH solutions under potentiostatic conditions.Negative reaction order was observed in dilute NaOH which transitioned to positive values as the passivation time increased and in the 1 M NaOH as well.The passive layers showed platelet morphology and the size of the platelets decreased with increase in the NaOH concentration.The hydrogen evolution reaction(HER)kinetics was not improved on the passive layer covered surface of the Mg-RE alloys in contrast to the improvements reported on the hydroxide covered pure magnesium.The electrochemical impedance increased with increase in the NaOH concentration in the solution treated condition of both Mg-RE alloys,whereas the overaged EV31A alloy showed a reverse trend.The passive layer of EV31A showed almost 100%higher charge carrier density than the film formed on the WE43C in the overaged condition.A better passivation behavior was observed in the solution treated condition than that in the overaged condition which could be attributed to the uniform distribution of the RE elements in the solution treated specimens.The WE43C alloy revealed better corrosion resistance in the alkaline solution than the EV31A alloy.

Concentration and separation of vanadium from alkaline media by strong alkaline anion-exchange resin 717

With strong alkaline anion-exchange resin 717 as the sorbent and NaOH solution as the eluent, a study on the sorption from alkaline solution and elution of vanadium（V）, silicon（iv）, and aluminium（III） was carried out. Different parameters affecting the sorption and elution process, including temperature, pH values as well as the ratio of resin to solution, were investigated. The results show that sorption degree of vanadium（V） increases with a decrease ofpH values, and V（V） ions are easier sorbed than Si（IV） and AI（III） ions under the same conditions. The sorption degree ofV（V）, Si（IV）, and AI（III） at pH 9.14 for 15 man are 90.6%, 33.5%, and 21.6%, respectively. Si（IV）, AI（III）, and V（V） ions sorbed on 717 resin were eluted by use of 2 mol·L^-1 NaOH solution; the desorption degree ofV（V）, Si（IV）, and AI（III） for 5 min are 81.7 %, 99.1%, and 99.3%, respectively.

Synthesis of Zeolites by Alkaline Activation of Fly Ash

In terms of mineral transformation, and chemical composition of acid-soluble component as a function of reaction time, the effect of alkaline solution on zeolite-like fly ash was studied by employing fly ash and NaOH solution as starting materials. When fly ash and 1-10 mol/L NaOH solution were processed at 100 degreesC for 24 h with 1:10 W/S ratio in a relatively closed system, powder XRD patterns of resulting products indicated the formation of various zeolites. Zeolite P crystallized early at low alkaline concentration, which was replaced then by zeolites X and A. At high concentration, hydroxy sodalite was the only new phase. Quartz, in fly ash and NaOH solution system, gradually dissolved, and mullite, however, remained stable. It was concluded that, with Al/Si and Na/Si finally reaching equilibrium in molar ratio, composition of starting mixtures affects the crystallization of zeolite from fly ash.

Electrolyte-gated SrCoO_(x) FET sensor for highly sensitive detecting pH in extreme alkalinity solution

The pH monitoring is significantly important in chemical industry,biological process,and pollution treatment.However,it remains a great challenge to measure pH in extreme alkalinity conditions.Herein,we employ an electrolyte-gated field-effect-transistor(FET)strategy using non-stoichiometric SrCoO_(x) with rich oxygen-vacancy defects as channel materials for detecting extreme alkalinity.The corresponding channel can provide effective oxygen-ion-migration sites for reversible transformation of OH-↔O_(2)-+H^(+)driven by electric field.The resultant electrolyte-gated FET sensor exhibits a sensitive linear response to high concentrations of alkaline solution,1–20 M.Significantly,the sensor has the ability to directly indicate the pH values ranging from 14.0 to 17.0 in consideration of ion-activity coefficient data.This work offers a great possibility for directly detecting base concentration as well as pH values in extreme alkaline solutions.

THE ELECTROCHEMICAL PREPARATION OF POLYPHENOL WITH CONDUCTIBILITY

Polyphenol film deposited on platinum foil can continuously grow with time during the electrolysis of a phenol solution consisting of 0.1 mol L-1 phenol, 3 mol L-1 NaOH and 0.5 mol L-1 Na2SO4, as has been proved by the methods of sweep potential, constant potential and constant current, and visible spectra during the electrolysis of phenol. A polyphenol film with thickness of 0.11 mm was obtained by the electrolysis of phenol at a constant potential of 0.70 V (versus Ag/AgCl with saturated KCl solution). Polyphenol film is inactive and stable in 2 mol L-1 H2SO4 solution, neutral solution and 3 mol L-1 NaOH solution and in the potential range between -0.95 and 1.35 V. The usable potential range is dependent on the pH value. Polyphenol has an ESR signal with a g factor of 2.0049. The conductivity of polyphenol is 1.2 x 10(-4) S cm(-1). In the solution of polyphenol dissolved in DMSO, the mobility of polyphenol anions is 8 x 10(-9) m(2) s(-1) V-1 at 20degreesC.

A New Protocol for Solubilization, Refolding and Purification of Recombinant Human Granulocyte Colony-stimulating Factor in Inclusion Bodies

Recombinant human granulocyte colony-stimulating factor （rhG-CSF） in inclusion bodies was solubilized by 8 mol/L urea solution and subsequently precipitated by acetone to improve its purity. After that, the precipitates were solubilized by sodium hydroxide solution containing 2 mol/L urea. Then the solubilized rhG-CSF was passed through a size exclusion chromatography for refolding and extensive purification, and further purified by a weak anion exchange chromatography. The purity and mass recovery of refolded rhG-CSF were 96.5% and 75.6%, respectively. The bioactivity was 8.4x10^7 IU/mg.

In-Situ Corrosion Monitoring of Scratched Epoxy Coated Carbon Steel in Saturated Ca(OH)2 with or without 3% NaCl by Scanning Electrochemical Microscopy and Electrochemical Impedance Spectroscopy

The present work is investigated the in-situ monitoring of local corrosion process of scratched epoxy coated carbon steel in saturated Ca(OH)2 with and without 3% NaCl using SECM and correlated with EIS. The results obtained from EIS analysis showed that the corrosion resistance of scratched epoxy coated carbon steel decreases in Cl- containing solution as the increase in wet/ dry corrosion cycles. This was indicated by decrease in film resistance (Rf) and charge transfer resistance (Rct), while the coated steel maintain the resistance values in saturated Ca(OH)2, most of which recovered after drying. The corrosion process was monitored using SECM by setting the tip potential at -0.70 V vs Ag/AgCl, where the consumption of dissolved oxygen occurred at the surface of test sample. The consumption of dissolved oxygen current (I’oxy-c) values was increased during the immersion in a solution with 3% NaCl. However, in wet/dry corrosion cycles, I’oxy-c was decreased due to the coverage of hydroxides/oxides at scratch area which suppressed the consumption of dissolved O2. It was found that the continuous decrease in corrosion was mainly attributed to continuous formation of corrosion products at anodic spots.

Solid-phase extraction gold from alkaline cyanide solution with quaternary ammonium surfactant

The solid-phase extraction（SPE） technique applied to the extraction of organic compound was creatively used as the extraction of inorganic gold in the paper.Two types of techniques were proposed and explored,namely the SPE and the liquid–liquid extraction（LLE） of the quaternary ammonium surfactant [cetytrimethyl ammonium bromide（CTMAB）,cetyl pyridine bromide（CPB）,benzyl dimethyl dodecyl ammonium chloride（BDMDAC）,and dodecyl trimethyl ammonium chloride（DTMAC）].The surfactant could react with Au（CN）2^- to form the ionic complex,and the compound could be extracted by SPE column of reversed-phase bonded silica gel.Hence,a new method of SPE was proposed to extract gold with these features of the high selectivity,the reliability,and the simplicity.The experimental result shows that the recovery rate of gold is more than 98 %,and the solid-phase extraction column is not easily damaged and it can be repeatedly used.The new method can be used as the extraction process of gold from alkaline cyanide solution as well.Besides,the paper also puts forward a new process of gold extraction.

Equilibrium and mechanism studies of gold(Ⅰ)extraction from alkaline aurocyanide solution by using fluorine-free ionic liquids

Solvent extraction based on ionic liquids is generally considered to be an environmentally benign and effective technology for gold(Ⅰ)recovery.The aim of this work is to study gold(Ⅰ)extraction from aurocyanide solution using fluorine-free ionic liquids[A336][SCN],[A336][MTBA]and[A336][Mal].Various factors that affect gold(Ⅰ)extraction(including concentration of ionic liquids,equilibrium pH,concentration of the modifier tributyl phosphate(TBP),reaction time and initial concentration of gold in an aqueous solution)were studied and optimized.The results indicate that the three Aliquat336-based ionic liquids all exhibit excellent behaviors for gold(Ⅰ)extraction.More than 99.8%of gold(Ⅰ)can be extracted from the aqueous phase into the ionic liquid phase.The gold-loaded ionic liquids were characterized using infrared spectroscopy and mass spectrometry to study the extraction mechanism of gold(Ⅰ).The results revealed that extraction of gold(Ⅰ)into the ionic liquid phase was based on an exchange reaction between the anion Au(CN)2-in aqueous solution and the anion SCN-in ionic liquid[A336][SCN].The logarithmic relationship between distribution coefficient and TBP concentration indicates that two TBP molecules are involved in the formation of the extracted complex.The extracted complex was determined to be A336^(+)·Au(CN)_(2)^(-)·2 TBP.In addition,the gold(Ⅰ)-loaded ionic liquids can be efficiently stripped using NH4 SCN,2-methylthiobenzoic acid and methyl maltol.The results establish that Aliquat 336-based ionic liquids have potential application prospects in gold(Ⅰ)recovery from cyanide solutions.

Fabrication of high-performance pervaporation composite membrane for alkaline wastewater reclamation

Pervaporation desalination has a unique advantage to recycle concentrated salt solutions.The merit can be applied to treat alkaline wastewater if the membrane has superior alkali-resistance.In this paper,we used polyethylene microfiltration membrane as the substrate and deposited a glutaraldehyde crosslinked sodium carboxymethylcellulose layer by spray-coating.Pervaporation flux of the composite membrane reached 352 kg·m^(-2)·h^(-1) with a sodium chloride rejection of 99.9%0.1%when separating a 3.5 wt-%sodium chloride solution at 70℃.The desalination performance was stable after soaking the membrane in a 20 wt-%NaOH solution at room temperature for 9 d and in a 10 wt-%NaOH solution at 60℃ for 80 h.Moreover,the membrane was stable in 4 wt-%sulfuric acid and a 500 mg·L^(-1) sodium hypochlorite solution.In a process of concentrating a NaOH solution from 5 to 10 wt-%at 60℃,an average water flux of 23 kg·m^(-2)·h^(-1) with a NaOH rejection over 99.98%was obtained.

Engineering heterostructure and crystallinity of Ru/RuS_(2) nanoparticle composited with N-doped graphene as electrocatalysts for alkaline hydrogen evolution

Crystalline engineering and heterostructure have attracted much attention as effective strategies to improve the electrocatalytic activity for hydrogen evolution reaction(HER).In this study,a new heterostructure catalyst(Ru/RuS_(2)@N-rGO)with low crystallinity was fabricated by a simple and low-temperature method for HER in alkaline solution,applying the Na_(2)SO_(4)as S source and polypyrrole as N source.Optimizing through the controllable crystalline engineering and composition ratio of Ru and RuS_(2),the Ru/RuS_(2)@N-rGO heterocatalyst at the calcining 500°C revealed highly efficient HER activity with overpotential 18 mV at a current density 10 mA/cm^(2)and remarkable stability for 24 h in 1.0 mol/L KOH.This work provides a facile and effective method in designing advanced electrocatalysts for HER in the alkaline electrolytes by synergistically structural and component modulations.